Summary: The polymer growth and the microstructure of the final polymer are greatly affected by mass transfer, especially in the early stages of polymerization. In the present work, the catalytic system (nBuCp)2ZrCl2/MAO immobilized over SiO2‐Al2O3 has been tested in ethylene‐1‐hexene copolymerizations using different amounts of comonomer. The catalytic activity shows a positive comonomer effect up to 1‐hexene concentration of 0.724 mol/L since larger amounts of 1‐hexene lead to a decrease in the activity. Copolymer properties analyzed by 13C NMR, GPC, CRYSTAF and DSC point to the presence of important amorphous regions in the growing polymer chains as the 1‐hexene concentration increases.In order to study the incorporation of 1‐hexene during ethylene polymerization, several experiments were performed with 0.194 mol/L of 1‐hexene, 5 bar of ethylene pressure and different polymerization times. The incorporation of 1‐hexene decreases slightly at polymerization times above 20 minutes. From cross‐sectioned SEM images it can be concluded that the presence of 1‐hexene helps catalyst fragmentation which could be related with the filter effect proposed by Fink.
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